Phosphorus oxychloride → HCID 54386943, compound

HRID 2059167Notes

Reaction equation

HRID 2059167 reaction equation
[C:1]([O-])(=O)C.[Na+].P(Cl)(Cl)(Cl)=O.[CH3:11][C@:12]12[CH2:29][CH2:28][C@H:27]3[C@@H:17]([C:18](=[O:30])[CH:19]=[C:20]4[C@:25]3([CH3:26])[CH2:24][CH2:23][CH2:22][CH2:21]4)[C@@H:16]1[CH2:15][CH2:14][C:13]2=[O:31]>C(Cl)(Cl)Cl.C(OCOCC)C>[CH2:1]=[C:21]1[CH2:22][CH2:23][CH2:24][C@@:25]2([CH3:26])[C:20]1=[CH:19][C:18](=[O:30])[C@@H:17]1[C@@H:27]2[CH2:28][CH2:29][C@@:12]2([CH3:11])[C@H:16]1[CH2:15][CH2:14][C:13]2=[O:31]

Participants

6

Reactant 3

HCID 24813Phosphorus oxychlorideHCID 517045Sodium AcetateHCID 15819093HCID 15819093, compound

Product 1

HCID 54386943HCID 54386943, compoundYield 80.6%

Reagents, catalysts & solvents 2

HCID 6212ChloroformSolventHCID 10024DiethoxymethaneSolvent

Procedure

A suspension of 1.0 g of sodium acetate in 30 ml of chloroform, 30 ml of formaldehyde diethylacetal, and 3.8 ml of phosphorus oxychloride is combined with 1.0 g of 5-androstene-7,17-dione and refluxed for 61/2 hours. Under agitation, a saturated soda solution is then added dropwise until alkaline reaction occurs in the aqueous phase. The organic phase is separated, washed with water, dried over sodium sulfate, and concentrated under vacuum. The crude product is purified on 200 g of silica gel with a hexane/ethyl acetate gradient (0-50% ethyl acetate), thus isolating 840 mg of 4-methylene-5-androstene-7,17-dione, mp 131.5°-132° C.

Workup

  1. temperaturerefluxed for 61/2 hours
  2. additionUnder agitation, a saturated soda solution is then added dropwise until alkaline reaction
  3. customThe organic phase is separated
  4. washwashed with water
  5. dry with materialdried over sodium sulfate
  6. concentrationconcentrated under vacuum
  7. customThe crude product is purified on 200 g of silica gel with a hexane/ethyl acetate gradient (0-50% ethyl acetate)

Sources & evidence

ORD record
ord-907b8953c00e4692a52742c52a70a3d7
Source dataset
uspto-grants-1982_03
Patent number
US04322349

Reaction notes

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